CN104130511A - Method for preparing chlorinated polyethylene foam material through irradiating vulcanization - Google Patents

Method for preparing chlorinated polyethylene foam material through irradiating vulcanization Download PDF

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Publication number
CN104130511A
CN104130511A CN201310157024.3A CN201310157024A CN104130511A CN 104130511 A CN104130511 A CN 104130511A CN 201310157024 A CN201310157024 A CN 201310157024A CN 104130511 A CN104130511 A CN 104130511A
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chlorinatedpolyethylene
foam material
radiation
chlorinated polyethylene
vulanization
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CN201310157024.3A
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刘伟
郝建钢
张玥
叶明旸
靳健乔
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TIANJIN INSTITUTE OF TECHNICAL PHYSICS
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TIANJIN INSTITUTE OF TECHNICAL PHYSICS
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Priority to CN201310157024.3A priority Critical patent/CN104130511A/en
Publication of CN104130511A publication Critical patent/CN104130511A/en
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Abstract

The invention belongs to a chlorinated polyethylene foam material and a preparation method thereof. The chlorinated polyethylene foam material comprises, by weight, 30-97% of chlorinated polyethylene, 0-57% of other olefin polymers, 2-20% of a foaming agent and 0.1-5% of an auxiliary vulcanizing agent. The preparation method is carried out in a manner of irradiating vulcanization and includes following steps: performing a melt blending moulding process to a mixture at 100-150 DEG C, carrying out the irradiating vulcanization process to a moulded subject with a radiation dosage being 10-200 kGy, and performing a high-temperature foaming process after the irradiation to obtain a finished product, wherein a normal-pressure foaming temperature is controlled between 180 DEG C to 350 DEG C and a pressurized foaming temperature is controlled between 180 DEG C to 300 DEG C. The invention has following beneficial effects: (1) the chlorinated polyethylene foam material is vulcanized through irradiating vulcanization so that a difficult problem that a molecular chain is liable to break during a chemical vulcanization process of the chlorinated polyethylene can be avoided; and (2) industrially large-scale production can be achieved.

Description

A kind of radiation vulcanization is prepared the method for chlorinatedpolyethylene foam material
Technical field
The present invention relates to the new preparation method of a kind of radiation vulanization chlorinatedpolyethylene foam material.
Background technology
The molecular structure of chlorinatedpolyethylene has the backbone structure identical with material polyethylene, and just the part hydrogen atom on backbone c atoms is replaced by chlorine atom.From the molecular structural formula of chlorinatedpolyethylene, it is a kind of saturated polymkeric substance, can regard the binary polymerization body of ethene, vinylchlorid, 1,2 Ethylene Dichloride as, and only, when cl content is very high, vinylidene chloride type chain link just likely exists.The ethene, vinylchlorid, 1,2 Ethylene Dichloride content and the difference arranged evenly separately that adopt different chloridization process Method and process condition products therefroms, the physicals that chlorinatedpolyethylene presents is also not identical.In addition, the different chlorinity of chlorinatedpolyethylene, molecular weight distribution are also the important factors that affects its performance.
The feature of chlorinatedpolyethylene
1) chlorinatedpolyethylene is a kind of saturated rubber, has outstanding heat oxygen aging resistance, ozone ageing, acid and alkali-resistance, pharmaceutical chemicals performance.
2) chlorinatedpolyethylene oil resistance is outstanding, and wherein resistance to ASTM1 oil, ASTM2 oiliness can be splendid, suitable with NBR; Resistance to No. ASTM3 oily excellent property, is better than CR, suitable with CSM.
3) in chlorinatedpolyethylene, contain chlorine element, there is splendid flame retardant properties, and have the anti-characteristic of dripping of burning.Itself and Sb system fire retardant, clorafin, Al (OH) 3the suitable ratio of three coordinates can obtain flame retardant properties fire retardant material good, with low cost.
4) chlorinatedpolyethylene is nontoxic, and or not containing heavy metal and PAHS, it does not meet environmental requirement completely.
5) chlorinatedpolyethylene has high filling properties, can make the product that meets various different performance requirements.The good processability of chlorinatedpolyethylene, mooney viscosity has the multiple trade mark available between 50-100.
The stretchiness of chlorinatedpolyethylene, weathering resistance, ozone resistance, thermotolerance, winter hardiness, flame retardant resistance, colour stability are good.At aspects such as heat-resisting, resistance to ozone, be better than chloroprene rubber.Ageing-resistant performance is better than epichlorohydrin rubber, paracril, chloroprene rubber and chlorosulfonated polyethylene rubber.There are the good flame retardant resistance most of corrosive mediums of ability simultaneously, as the solution of the mineral acid of high density, alkali and salt, but the medicine of powerful oxidation corrosion resistance agent and solvation not, as concentrated nitric acid, chromic acid, perchloric acid and organic amine etc.Except above-mentioned advantage, processing characteristics is good, can make the rubber item of smooth surface, rounding.This has good tint permanence and ageing resistance as pure white powder, can make beautiful in colour and durable rubber item.
The energetic ray that rumbatron produces has following characteristics: polymkeric substance and the monomer of (1) any shape all can be used, and can complete chemical method and be difficult to the reaction of carrying out.(2) ray energy is high, and penetrativity is strong, and reaction can be deep into material inside.(3) operation is simple, and the reaction times is short, and stability is high.Do not need linking agent and initiator, do not need to carry out aftertreatment.Rumbatron high-power electron beam utilizes charged particle to carry out radio polymerization to material, has non-secondary pollution, can serialization process for processing etc. advantage.For the further industrialized development of radiation vulanization chlorinatedpolyethylene foam material provides possibility.
Patent 200710057856.2 provides a kind of polypropylene foam material and manufacture method thereof of belonging to.Polypropylene foam material, its component and weight percent content are as follows: acrylic resin 30～97%, other olefin polymer 0～57%, whipping agent 2～20%, additional crosslinker 0.1～5%.Manufacture method is to adopt Radiation Crosslinking Method: mixture, 110～160 ℃ of melt blending moulding, is carried out to radiation crosslinking by forming composition, and radiation dose is 10～200kGY; After irradiation, be finished product again through high temperature foaming, normal pressure blowing temperature is controlled at 200～350 ℃; Pressure expansion temperature is controlled at 200～300 ℃.
Patent 201210125819.1 provides a kind of irradiated crosslinked chlorinated polyethylene insulated flexible cable, this cable comprises cable core, described cable core forms by several wire core is stranded, the tinned wird stranded conductor of described core in the middle of comprising and be successively set on conductor isolation layer and the chlorinated polythylene insulating layer outside this conductor, the gap-fill in cable core has weighting material, at cable core, sets gradually cable core sealing coat and outer jacket outward.Structure of the present invention meets working conditions to high electrical property, and the requirement of oil resistant, resistance to ozone, weather, heat-resisting, fire-retardant and high-intensity performance has the function of energy-conserving and environment-protective simultaneously.
This project of this patent substitutes traditional foam material with the chlorinatedpolyethylene of excellent performance.The mode that replaces traditional vulcanization of rubber with radiation vulanization.
Summary of the invention
Radiation vulanization chlorinatedpolyethylene foam material, is characterized in that component and weight percent content are as follows:
Chlorinatedpolyethylene 30～97%,
Other olefin polymer 0～57%,
Whipping agent 2～20%,
Cocuring agent 0.1～5%.
The preferred component of the present invention and weight percent content are as follows:
Chlorinatedpolyethylene 50～80%,
Other olefin polymer 15～45%,
Whipping agent 3～17.5%,
Cocuring agent 1～3%.
As required, in formula system, also can add the common additives for plasticss such as oxidation inhibitor, lubricant, tinting material, filler.
The manufacture method of chlorinatedpolyethylene foam material of the present invention, is characterized in that adopting radiation vulcanizing method.Concrete grammar is as follows:
(1) component mixed by content proportioning or be first a granulated into respectively masterbatch and evenly mix again;
(2) by mixture 100～150 ℃ of melt blending moulding;
(3) forming composition is carried out to radiation vulanization, radiation medium includes but not limited to: alpha-ray, β ray, gamma-rays, X ray, high-power electron beam or ultraviolet ray, and radiation dose is 5～60kGy;
(4) after irradiation, be finished product again through high temperature foaming, normal pressure blowing temperature is controlled at 200～350 ℃; Pressure expansion temperature is controlled at 200～300 ℃.
The multiplying power of the foam material described in the present invention can be adjusted by adjusting the addition of whipping agent, and the multiplying power that can reach is 4～36 times.
The technical process that the present invention adopts is:
(1) matrix resin evenly mixed by proportioning with chemical foaming agent, cocuring agent and other auxiliary agent or be first a granulated into respectively masterbatch and evenly mix again.
(2) by the mixture melt blending moulding of (1) step, may be molded to sheet material or profiled material.Blending equipment can be used mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.Stable for guaranteeing in moulding process, blend mold temperature should be controlled at 100～150 ℃, is preferably 125～150 ℃.
(3) forming composition of previous step is carried out to radiation vulanization.Radiation medium includes but not limited to: alpha-ray, β ray, gamma-rays, X ray, high-power electron beam or ultraviolet ray, be preferably the high-power electron beam of high-energy electron accelerator; Radiation dose is 5～60kGy, is preferably 10～40kGy.
(4) after irradiation, through high temperature foaming, be product again.Foam device can adopt normal pressure foam device as horizontal foaming furnace, vertical foaming stove, salt bath foaming furnace etc., also can adopt pressure expansion device as moulded from foam equipment etc.Normal pressure blowing temperature is controlled at 200～350 ℃, preferably 240～310 ℃; Pressure expansion temperature is controlled at 200～300 ℃, is preferably 230～260 ℃.
In the present invention, whipping agent used requires decomposition temperature at 185.260 ℃, is preferably 190-250 ℃.Comprise Cellmic C 121 (AC), p-toluene sulfonylsemicarbazide (TSSC), 5. phenyltetrazole (5.PT), N, N '. the mixture of one or more in dimethylene pentamethylene tetramine (DNPT), is preferably Cellmic C 121 (AC).
In the present invention, cocuring agent used is a kind of two functional groups or polyfunctional compound, including but not limited to trimethylolpropane trimethacrylate (TMPTMA), Viscoat 295 (TMPTA), dihydroxy methylpropane dimethacrylate (DMPDMA), triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), 1,4. butylene glycol diacrylate (BDDA), 1, the mixture of one or more in 6 one hexanediyl esters (HDDA), preferably trimethylolpropane trimethacrylate (TMPTMA).
Effect of the present invention:
(1) radiation vulanization chlorinatedpolyethylene foam material of the present invention is used method of radiating to vulcanize, a difficult problem for molecular chain easy fracture in the time of can breaking away from chlorinatedpolyethylene baking;
(2) the present invention can realize industrialized mass production.
Embodiment
With embodiment, further describe the present invention below, but scope of the present invention is not subject to the restriction of these embodiment.
The method that the embodiment of the present invention adopts the following is:
(1) matrix resin evenly mixed by proportioning with chemical foaming agent, cocuring agent and other auxiliary agent or be first a granulated into respectively masterbatch and evenly mix again.
(2) by the mixture melt blending moulding of (1) step, may be molded to sheet material or profiled material.Blending equipment can be used mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.Stable for guaranteeing in moulding process, blend mold temperature should be controlled at 100～150 ℃, is preferably 125～150 ℃.
(3) forming composition of previous step is carried out to radiation vulanization.Radiation medium includes but not limited to: alpha-ray, β ray, gamma-rays, X ray, high-power electron beam or ultraviolet ray, be preferably the high-power electron beam of high-energy electron accelerator; Radiation dose is 5～60kGy, is preferably 10～40kGy.
(4) after irradiation, through high temperature foaming, be product again.Foam device can adopt normal pressure foam device as horizontal foaming furnace, vertical foaming stove, salt bath foaming furnace etc., also can adopt pressure expansion device as moulded from foam equipment etc.Normal pressure blowing temperature is controlled at 200～350 ℃, preferably 240～310 ℃; Pressure expansion temperature is controlled at 200～300 ℃, is preferably 230～260 ℃.
In the present invention, whipping agent used requires decomposition temperature at 185.260 ℃, is preferably 190.250 ℃.Comprise Cellmic C 121 (AC), p-toluene sulfonylsemicarbazide (TSSC), 5. phenyltetrazole (5.PT), N, the mixture of one or more in a N ' dimethylene pentamethylene tetramine (DNPT), is preferably Cellmic C 121 (AC).
The invention has the beneficial effects as follows: 1) the present invention has selected a kind of new foam material, and this foam material has many excellent properties; 2) the present invention uses the method for radiation vulanization rubber pange, has shortened the reaction times, has simplified reaction process.

Claims (8)

1. a radiation vulanization chlorinatedpolyethylene foam material, is characterized in that component and weight percent content are as follows:
Chlorinatedpolyethylene 30～97%,
Other olefin polymer 0～57%,
Whipping agent 2～20%,
Cocuring agent 0.1～5%.
2. a radiation vulanization chlorinatedpolyethylene foam material, is characterized in that component and weight percent content are as follows:
Chlorinatedpolyethylene 50～80%,
Other olefin polymer 15～45%,
Whipping agent 3～17.5%,
Cocuring agent 1～3%.
3. claim 1 and radiation vulanization chlorinatedpolyethylene foam material claimed in claim 2, is characterized in that: the cl content of described chlorinatedpolyethylene is 30～45%.
4. claim 1 and radiation vulanization chlorinatedpolyethylene foam material claimed in claim 2, is characterized in that: other described olefin polymer comprises: the mixture of one or more in Low Density Polyethylene, high density polyethylene(HDPE), linear low density polyethylene, metallocene linear-low density polyethylene, ethene, acetate ethylene copolymer, polyolefin elastomer, vinylbenzene, divinyl, styrene block copolymer, hydrogenated styrene, divinyl, styrene block copolymer or terpolymer EP rubber.
5. claim 1 and radiation vulanization chlorinatedpolyethylene foam material claimed in claim 2, it is characterized in that: described foaming agent decomposition temperature is between 185～260 ℃, and comprise Cellmic C 121, p-toluene sulfonylsemicarbazide, 5 one phenyltetrazoles or N, the mixture of one or more in a N ' dimethylene pentamethylene tetramine.
6. claim 1 and radiation vulanization chlorinatedpolyethylene foam material claimed in claim 2, it is characterized in that: described cocuring agent is a kind of two functional groups or polyfunctional compound, comprise trimethylolpropane trimethacrylate, Viscoat 295, dihydroxy methylpropane dimethacrylate, triallyl isocyanurate, triallyl cyanurate, 1,4. butylene glycol diacrylate or 1, the 6. mixture of one or more in hexanediyl ester.
7. the manufacture method of claim 1 and radiation vulanization chlorinatedpolyethylene foam material claimed in claim 2, is characterized in that step is as follows:
(1) component is directly mixed or is first a granulated into respectively masterbatch by proportioning evenly mix again;
(2) by mixture 100～150 ℃ of melt blending moulding;
(3) forming composition is carried out to radiation vulanization, radiation absorbed dose is 10～200kGy;
(4) after irradiation, foam through high temperature, normal pressure blowing temperature is controlled at 180～350 ℃ again; Pressure expansion temperature is controlled at 180～300 ℃.
8. the manufacture method of claim 1 and radiation vulanization chlorinatedpolyethylene foam material claimed in claim 2, it is characterized in that: forming composition is carried out to radiation vulanization, radiation medium includes but not limited to: alpha-ray, β ray, gamma-rays, X ray, high-power electron beam or ultraviolet ray, radiation dose is 10～200kGy.
CN201310157024.3A 2013-05-02 2013-05-02 Method for preparing chlorinated polyethylene foam material through irradiating vulcanization Pending CN104130511A (en)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN105670144A (en) * 2016-01-28 2016-06-15 泉州三盛橡塑发泡鞋材有限公司 Rubber type chlorinated polyethylene foam material and preparation method thereof
CN107880410A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of fretting map Precasting synthetic surface track
CN107880409A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of bumper and absorbing shock plastic grains and preparation method
CN107880403A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of ageing-resistant environmentally friendly lawn particle
CN107880412A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of preparation method of high-elastic environment friendly plastic rubber runway particle
CN107880411A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of fretting map environmental protection lawn particle
CN113105683A (en) * 2021-04-09 2021-07-13 杭州科佳新材料股份有限公司 Oil-resistant super-soft polyethylene material and preparation method thereof

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JPS572342A (en) * 1980-06-04 1982-01-07 Furukawa Electric Co Ltd:The Rubberlike foam and its preparation
CN1918236A (en) * 2003-12-24 2007-02-21 陶氏环球技术公司 Free-radical crosslinkable polymers: improved process for crosslinking and compositions

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JPS572342A (en) * 1980-06-04 1982-01-07 Furukawa Electric Co Ltd:The Rubberlike foam and its preparation
CN1918236A (en) * 2003-12-24 2007-02-21 陶氏环球技术公司 Free-radical crosslinkable polymers: improved process for crosslinking and compositions

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105670144A (en) * 2016-01-28 2016-06-15 泉州三盛橡塑发泡鞋材有限公司 Rubber type chlorinated polyethylene foam material and preparation method thereof
CN105670144B (en) * 2016-01-28 2018-11-13 泉州三盛橡塑发泡鞋材有限公司 A kind of rubber-type chlorinated polyethylene expanded material and preparation method thereof
CN107880410A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of fretting map Precasting synthetic surface track
CN107880409A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of bumper and absorbing shock plastic grains and preparation method
CN107880403A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of ageing-resistant environmentally friendly lawn particle
CN107880412A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of preparation method of high-elastic environment friendly plastic rubber runway particle
CN107880411A (en) * 2016-09-29 2018-04-06 青岛科技大学 A kind of fretting map environmental protection lawn particle
CN107880412B (en) * 2016-09-29 2021-02-09 青岛科技大学 Preparation method of high-elasticity environment-friendly plastic track particles
CN113105683A (en) * 2021-04-09 2021-07-13 杭州科佳新材料股份有限公司 Oil-resistant super-soft polyethylene material and preparation method thereof

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